Condensation product of aldehydes and carbamidomethylamino triazines and method of preparing the same



- phenyl, allylphenyl,

, chlormethyl,

Patented Jan. 18 1 944 UNITED STATES PATENT v OFFICE CONDENSATION PRODUCT F ALDEHYDES AND CARBAMIDOMETHYLAMINO TRIA- ZINES AND METHOD OF PREPARING THE SAME Gaeta'no F. DAlelio, Pittsfleld, Mass assignor' to General Electric Company, a corporation of New York No Drawing. Application Dccember3,

Serial No. 421,493

. (Cl. 26il-t9) 12 Claims.

This invention relates to new condensation products and to method of making the same. Generally, it is concerned-with resinous compositions prepared from novel compounds containing imino, amino, imido, and amido groups. Specifically, it is concerned with, and has as its principal object the preparation of, resinous compositions obtained as condensation products of ingredients comprising an aldehyde and certain novel substituted or unsubstituted carbamidomethyl derivatives of 2,4,6-triamino 1,3,5 triazines having the general structural formula in which Y represents oxygen or sulphur, at least one R represents hydrogen and the other (Rls represent hydrogen, a monovalent hydrocarbon radical or a monovalenthalogenohydrocarbon radical, R aliphatic, carbocyclic or aromatic hydrocarbon radical of not more than six carbon atoms and R." represents hydrogen or any monovalent hydrocarbon radical, whether saturated or unsaturated, substituted or nuclear, etc.,' and n is an integer and is at least representshydrogen or a monovalent.

unsubstituted, aliphatic car- 5. bocyclic, aryl, or heterocyclic, monoor poly-' 1 and not more than 3. Examples of suitable hydrocarbon radicals represented by R and R" are aliphatic (e. 8. methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, butenyl, amyl, hexyl, allyl, etc); including cycloaliphatic (e. g. cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl,

cycloheptyl, etc.); aryl (e. g. phenyl, diphenyl, naphthyl, etc.); aliphatic substituted aryl e. g. tolyl, xylyl, ethylphenyl, propylphenyl, isopropyletc.) aryl substituted aliphatic (e. g. benzyl, phenylallyl, phenylpropyl,

etc); and their. homologues, as well as those groups with one or more of their hydrogen atoms substituted by a halogen. Specific examples or halogeno-substituted hydrocarbon radicals are chlorcyclohexyl, chlorphenyl, diethyl chlorphenyl, pheny1 chlorbromethyl, bromtolyl, etc. Preferably R, R and R" in the above formula are hydrogen.

chlorphenyl,

hereinbefore indicated, with p aqueous solution of a zfihd triaxnino 1,3,5 triaainc it The novel substituted or unsubstituted carba midomethyl derivatives of ZAfi-triamino 1,3,5

triazine represented by the above formula may be prepared by reacting, at room temperature, a

concentrated aqueous solution of a substituted "or unsubstituted mono-carbinol urea 01' thiourea of the formula R .Y a n it tat-(Lora the various aroups a concentrated wherein R, R and-Y represent containing sumcient hydrogens on each of the amino groups that after reaction with the mono carbinol urea each of the amino groups will con 'tain at least one reactive hydrogen. The mol rav tie in which the two reactants are mixed will de pend upon the desired product. Thuafor example, when they are mixed in a mol ratio of int,

the reaction product is a monocarbamldometbyl derivative of the formula NHR , N" N nni-ornmonw-nng-NHR" N wherein R, R, R", and Y represent the groups above indicated.

As a more specific example of the preparation ,of my novel starting materials, a cold concentrated solution of 2 mols 01 an unsubstituted mono-methylol urea reacts with a cold concentrated solution or 1 mol of 2,4,6-triamino 1,3,5- triazine to form the di-carbamidomethyl derivative having the formula Examples of monocarbinol ureas, other than I monomethyioi urea, which may be used are:

methylol thiourea, methylcarbinol urea. and thio'. "5 urea','etn 1carbmo1 urea and thiourea, proplycarous substitutable hydrogens ureas, dimethylol ureas,

ethyl. propyl. isopropyl, butyl,

. ailyl, crotyl, l-chlorallyl,

binol urea and thiourea, methylol phenyl ureas and thioureas, methylol allyl ureas and thioureas, methylol diphenyl ureas and thioureas, etc.

Examples of substituted 2,4,6-triamino 1,3,5-

the water at or below room temperature under.

atmospheric or subatmospheric pressures. Alternatively, in! to the aqueous solution of the reaction prodnot a suitable water-miscible precipitant tor the reaction product, which precipitant is incapable o! reacting with the desired product at operating temperatures.

The resulting compounds may be resiniiled by reaction with aldehydes or aldye engendering substances, preferably under the influence of heat, the unsubstituted derivatives obtained by reacting 1, 2, or 3 mols of urea with lmol of 2,4,6 triamino 1,3,5-triazine being most easily resinified .under such conditions. The relative ease of resinitlcation decreases with increased replacement of the variby hydrocarbon radimay be accomplished by heating the reactants alone, in inert mediums, or in inert solvents such as water. Resinifica tion may be accelerated by the addition or presence of basic materials, acidic materials, neutral, acid, or alkaline salts. Reactive media may likewise be used to achieve resiniilcation as hereinafter shown.

This novel class of organic compounds may be mixed with resin intermediates containing carbinol (CRaO1-1) groups, such as monomethylol phenol methylols, the methylols of cyclic amidines, e. g. methytlol melamines, methylol guanazoles, etc.; then coor inter-resinifled alone or in the presence of other modifying bodies to give intercondensed resins.

The novel compounds of this invention, particularly the highly substituted compounds, may be used as plasticizers for many resins. In many cals. Resinification cases they themselves become resinous during the plasticizing process, while in other cases they condense with the other resinous intermediate during manufacturing operations. Specifically, these materials may be used (1) unconverted as plasticizers, (2) partly or completely converted as plasticizers, (3) partly or completely interoondensed to exert a plasticizing effect. The final and intermediate resins prepared from the novel materials of this invention alone or with the modifications expressedherein are extremely compatinatural'or synthetic resins in his with many other ultimate stages.

their intermediate or Before, during, or alter the resinincation proc-' see, the reaction between the aldehyde or mixture of aldehydes and the novel compounds of this invention may be modified by the presence suitable amounts of a large class of compounds, tor example, hydroxy compounds, e. g. methyl, amyi, tertiary amyi. benzyl, iuriuryl, tetrahydroiuriuryl, cyclohexyl. phenethyl, naphthyl, polyvinyl, allyl, methpropargyl, fl-ehlorallyl.

the product may be recovered by addmonomethylolurea or thiocinnamyl, alcohols, eta, glycol, diethylene glycol, triethylene glycol, polyethylene oxide, glycerine, pentaerythritol, saligenin, phenol, cresol, xylenoi, resorcinol, catechol, pyrogallol, etc., chlorohydrin, epichlorohydrin, nitrobutanol, diacetone alcohol, ethylene oxide, propylene oxide, etc., ammonia and its amino, amido, or imino compounds, e, g. methylamine, dimethylamine, hydroxylamine, hydrazine, phenyl hydrazine, diamylamine, stearyl amine, cyclohexyl amine, aniline, di-phenylamine, diaminobenzene, triaminobenzene, aminophenol, nitro aniline, piperazine, ethanolamine, di-isopropanolamine, triethanolamine, propanolamine, ethylene diamine, iormamide, acetamide, propionamide, lauramide, acrylic amide, methacrylic amide, atropic amide, malonic diamide, itaconic diamide, succinic diamide, citraconic triamide, benzamide, phthalic diamide, phthaiimide, benzosulfimide, aminobenzene sulfonamide, benzene disulfonamide, benzene trisulfonamide, anthranilic esters, anthranilamide, salicylamide, para-phenyl benzene sulionamide, tolyl amide, etc.; the amino 1,3,5-triazines, e. g. 2,4,6-triamino 1,3,5'-triazine, 2-amino 1,3,5-triazine, 2,4-diamino 1,3,5-triazine; the diazines, e. g. 2,4,6-triaminopyrimidine the diamino pyrimidine thio ethers; the amino 1,2,4-triazones, e. g. guanazole, phenyl guanazole, dihydrazino 1,2,4-pyrrodiazole, guanazo-guanazole, imidurazo-guanazole, the amino 1,2-diazoles, e. g. 3,5-diaminopyrazole, the urea as lactic esters, hydroxy isobutyric esters, acetoacetic ester, malonic esters, etc.

The final and intermediate resins and condensation products prepared from the novel mate-.-

-' rials of this invention alone or with the modifications already expressed are extremely compatible with many other natural or synthetic resins in their intermediate or ultimate stages.

This novel class of compounds, when reacted with aldehydes, alone or with modifications, will form self-curing aminoplasts by condensation with curing reactants, such as chloroacetonitrile,

nitrourea, glycine, aminopropanol hydrochloride, mono-,dior tri-chloroacetamides, alpha; betadibromopropionitrile, alpha, beta-dichloropropionitrile, alpha-methyl, alpha, beta-dichloropropionitrile, amino-acetamide hydrochloride, ethylene diamine monohydrochloride, sulfamic acid. chloroacetyl urea, citric diamide, phenacyl chloride and others mentioned, for example in my copending applications Serial No. 346,962, filed July 23, 1940, and Serial No. 354,395, filed August 27, 1940, both 01 which applications are assigned-to the same assignee as the present invention.

" assets:

Examples of other substances yielding alkaline.

aqueous solutions may be used in obtaining alkaline conditions for the initial'condensatlon reaction are alkalis such as sodium. P tassium and calcium hydroxides, sodium and potassium carbonates, mono-, diand tri-amines, etc. Best .results are obtained by causing the condensation reaction between the primary components to take place in the presence oi. a primary condensation catalyst and a secondary condensation catalyst. To obtain condensationproducts havin: optimum timeshould be a member of the class consisting of (1) nitrogen-containing basic tertiary compounds that are aldehyde-non-reactable, e. g. tertiary amines such as trialkyl (for example, trimethyl,

triethyl, etc.) amines, triaryl (for example, tri-,

phenyl, etc.) amines, etc., and (2) nitrogen-corrtaining basic compounds that are aldehyde-reactable, for instance ammonia, primary amines,

' (e. g., ethyl amine, propyl amine, etc.) and secondary' amines (e. g. dipropyl amine, dlbutyl amine, etc.) Catalytic reactants that may be used include substances such as tri-carbamido methyl amine N(CH2NHCONH:)3 or other sub- 1 ordinarily is used in an. amount less than the amount of primary catalyst, should be a fixed alkali, for instance a carbonate, cyanide or hydroxide of an alkali metal -.(e. g. sodium,- potassium, lithium. etc.). a i

Various ways may be employed for eflecting initial reaction between the components. For

example, I may .flrst mix all the reactants and eiiect condensation between the mixed reactants in the presenceor absence addition agents, for instance condensation catalysts, fillers, other natural or synthetic resinous bodies, solvents, diluents, etc. Alternatively, I may first condense either my compound, or some other aldehyde reactable material such as a urea, a phenol, a melor storage-stability characteristics, I have found that the primary catalyst while hot but of the syrup with 51 thos skilled in the art from the following exam ples covering the preparation 01' resinous prodnote from the mono-, diand tri-carbamidomethyl derivatives of melamine, which derivatives, for brevity, will be designated respectively as the mono-derivative, di-derivative or tri-derivative.

Example 1 Mol ratio Parts by "5113? weight Azxneous mono'derivativc (57% concentra- 122. 5 Aqueous formaldehyde. 84.8

The aqueous formaldehyde used in this and the following examples contained approximately 87.5 per cent CHaO. The mono-derivative and the formaldehyde solution were mixed and re-.

fluxed at the boiling temperature of the mass for 15 minutes to produce a syrup which was clear which precipitated on cooling to room temperature. 'The syrup had a pH of 7.5 and its cure on a hot plate at 135 C. was comparatively slow. The addition of small amounts (about 0.5 per cent) of curing agents such as vchloroacemide or alpha, beta-dichloropropionitrile greatly accelerated the cure. A molding compound made by mixing 150 parts by weight parts by weight of alpha flock and drying the'mixture at 70 C. had good flow and an excellent cure when molded for 5 minutes at 135 pounds per square inch. The molded piece was mine or the like, with a suitable aldehyde and thereafter at any-stage oi the original reaction.

I may add the remaining aldehyde-reactable in-' gradient or ingredients. or I may condense or partially condense my novel compoundswitli an ,tion to proceed further. Still other ways may be employed in combining thecc'mponenta'in 'pro-J duclng the modified or unmodified products or as will readily be understood by 78 from 1'40 Example 2 Parts by weight Aqueous (ii-derivative (66% concentration) i Formaldehyde 5 were refluxed for 15 minutes to produce a syrup which was clear while hot but out on cooling to had'a pH of 7.25

which precipitated room temperature. The syrup and had a good cure at 135 0., which cure was accelerated by the addition or small amounts oi chloroacetamide. A molding compound prepared in the manner set forth in Example 1 from parts by weight of resin syrup and as parts of alpha flock exhibited excellent moldabi1it'y and good flow.

The molded product resembled that obtained in Example 1.

Example 3 Parts by weight same tri-derivstive (68.6% concentrawere refluxed for 15 minutes to obtain a syrup" .which was. clearboth atelevated and room tem-'- peratures. IthadapI-Ioi'dfl. Ithad agoodcure' alone when tested at 0. with small addioi alpha,beta-dichloropropionltrile,it had an excellent cure,

curing quickly to a hard state. Mol

ding compounds prepared as in Example .1 parts syrup and 50 parts by weightpt (3. under a pressure of 6,000.

alpha flock had excellent flow and cure characteristics and the molded products were comparable with those obtained in the previous examples.

Example 4 Using the same procedure and proportions as in Example 1, the same reactants were heated togather with an aqueous solution of 0.01 mol (0.14 part) sodium hydroxide. The syrupy product was clear both at elevated and room temperatures and contained about 42 per cent resin solids. It had a pH about one point higher than the pH of the syrup of Example 1. The syrup did not cure alone at 135 C., but had an excellent, prolonged cure when modified by the addition of a small amount of chloroacetamide or alpha, beta-dibromopropionitrile. When the syrup was added to a liquid phenol-formaldehyderesin freed of catalyzing bases and salts as a modifier therefor in the proportion of 1 part syrup to 9 parts varnish (based on the resin solid contents of therespective materials) the product had a stroke cure time at 150 C. of 80 seconds as compared with 108 seconds for the unmodified varnish.

Comparable results were obtained with sodium hydroxide-catalyzed diand triderivative resins in which the proportions of the reactants were the same as in Examples 2 and 3. The rate of cure of the diand triderivatives, both alone and with curing accelerators, increased progressively with the increase in the number of carbamidomethyl groups on the melamine nucleus. These resin syrups also had similar effects as modifiers for the above-mentioned synthetic liquid phenolic resin.

Example 5 Resin syrups were prepared from the mono-, diand tri-derivatives as in Example 4, using catalyst mixtures consisting of 0.01 mol sodium hydroxide and 0.12 mol ammonia (aqueous solution). The syrup obtained from mono-derivative had a very slow cure while the syrup obtained from the t'ri-derivative cured faster and had an excellent cure with chloroacetamide. Molding compounds were prepared from the three syrups using 55 parts syrup (based on the solids content thereof), 45 parts alpha flock and 1 part chloroacetarnide. All three compounds exhibited good flow and excellent cure. The molded products were light-colored and possessed hard, shiny surfaces.

Example 6 M01 ratio Parts by (approx.) weight Aqueous mono-derivative (57% concentraon) 1 63.7 Acrolein 3 29.6

assaoae the tri-derivative and the acrolein, a violent reaction occurred and the syrup turned to a clear.

yellow, thick mass. A sample of this mass melted when placed on the hot plate at 135 C. and was slowly self-curing at that temperature. The final inlus'ible resin was hard and yellow.

Example 8 and tri-derivatives were reacted with formalde hyde in the presence of a catalytic reactant consisting of 0.1 mol (in aqueous-solution) of a tri(mono-carbinelureidomethyl) amine having the formula N(CH2NHCONCH2OH)3. This aldehyde-reactableamine derivative is more fully described in my copending application Serial No. 409,018, filed August 30, 1941. The syrupy products cured alone at 135 C. Curing agents, such as chloroacetamide or alpha, beta-dichloropropionitrile accelerated the curing rates. Molding compounds containing 55% resin syrup (on solids basis) and 45% by weight of alpha flock exhibited excellent moldability and good flow and cure with or without the addition of 1% chloroacetamide.

were refluxed for 15 minutes. The syrupy product was clear while hot and precipitated out on cooling. It had a pH of 7.65 and a slow cure alone at 135 C. With chloroacetamide a good, acceler ated cure was obtained.

Example 10 M01 ratio Parts by (approx) weight Aqueous di-derivative conccntration).. l 75.7 55 Urea l 11.1 Aqueous formaldehyde 7 103.6 N aOli (dissolved in water) 1 0.01 0. 074

were refluxed for 15 minutes to produce a syrup which was clear while hot and also on cooling. It

had a pH of 8.0 and cured slowly at 135 C.

To 180 parts of syrup were added 0.75 part chloroacetamide. Sheets of 10 mil all-rag paper were dipped in this syrup, dried at C. and laminated at C. and 2000 pounds per square inch pressure for V2 hour. Excellent laminated products, which were light colored and translucent were obtained. Similar products were obtained by substituting 'an equimolar amount of the tri-derivative for the di-derivative and ingresising the mol ratio of formaldehyde from '7 Example 11 Example 10 was repeated using an equivalent amount of thlourea in. place of the urea called for chloroacetamide', the

. very translucent, hard and shiny.

Aq l eous mono-derivative (57% .ing. It had pH=8.3. At 135' yellow.

containing in the formulation 01' Example 10. The product had an excellent care at 135 C. Molding. compounds prepared from 55 parts syrup (on resin solids basis), 1 part chloroaceta'mide. and

45 parts alpha flock had good moldabi lity andilow and cured to hard. opaque masses. Comparable molding compounds were Example 12 Moi ratio Parts by (approx) weight Aqueous diderivative (66% concentration)., 1 75. 7 Aqueous formaldehyde 5 88. 8 Para toluene sulionamide l6 l5. 8 NnOH (in 3.5 parts water) 0.01 0. 074

were refluxed for I clear while hot but precipitated on cooling. At 135 C. it had a good, but prolonged. cure. With cure was excellent with a long, tack stage. A molding compound prepared from 55 parts syrup (on resin solids content) and 45 parts alpha :dock was dried at 70 C. and molded at 135 C. and 6000# pressure for 5 minutes. The compound had excellent moldability, good flow and cure and the molded product had a hard surface and was light-colored.

Moi ratio rim by ump) w isht Aqueous trl-derivative 68% concentration). i 73.0 Para toluene sulfonamide M 12.5 Aqueous formaldehyde 8 03.0 NaOH (in'2.5 parts water) 0.01 0. 068

were refluxed for 15 minutes. The clear while hot and also on cooling. At 135' had a very slow and rather was 0. it sott cure. With chlosome also prepared from the monoand tri-derivati es. 1

Example 14 Moi ratio Parts by (approx) weight Aqueous (ii-derivative (66% concentration) It 'idiiy' ueous orms e N205 (dissolved in 3.5 parts water) poet-mwere refluxed for 15 minutes. The resultant syrup was clear while hot and also on cooling minutes. The syrup was so were refluxed for 15 minutes.

and had a pH of 8.15. At 135 C. it cured alone. A molding compound prepared'trom 180 parts by weight of syru and parts alpha flock was oven dried at C. and molded at C. and 6000#' pressure for 5 minutes. The compound had excellent flow and hard cur The molded piece had a very light color and a shiny surface. This was considered a cry good molding composition.

Example 15 M01 ratio Parts byf (approx) weight mmofliyioi (metal 11% iiQb'iIII I 270 Aqueous NH: (28%). 0. 3

while hot but precipitated on cooling and had a pH of 6.8. The cure alone 'at 135 C. was very slow and soft. With chloroacetamide an accelerated excellent cure was obtained.

A molding compound from parts syrup (on resin solids basis) 59 parts alpha flock and 0.14 part chloroacetamide had good flow and cured to a translucent solid with a yellow cast.

roacetamide the cure was accelerated but was still prolonged. An oven-dried molding compound containing 55 p rts 7 1!]! (on solid basis), 1 part chloroacetamide and 45 parts alpha. flock was molded at 135 C. and 8000# pressure for 5 minutes. Thi compound had excellent moldabillty and good flow and the molded product was Example 1 and tic t n) 31 "ia't" queous orma e NeOH (in 7 parts wild)"- minutes to form a resinous while hotandalso on cool- C. it did not cure a slow cure was were" refluxed for l5 syrup that was clear alone. With obtained.

A molding compound from 55 resin solids-content), 45 parts \Illhl flock and 2 parts chloroacetamide had and good flow.

chloroacetamide,

The molded product was slightly One part chloroacetami to impartgood moldability' molding compositions prepared for resin syrups equivalent amounts of the dblnd triderivatives.- r

de'was sumcient and cure to such m were refluxed for 15 minutes tions.

parts s up (on I excellent moldability etamide greatly N cure Example 16,

M01 ratio Partsby '(approx.) I weight Aqueous mono-derivative (67% ecncentre'-' tion) 1 1%.5 'lrimethylol melamine 1 151. 5 Aqueous iormaldeh de.... .6 169.!- Aqueous NH: (28% 7 35 H 0.75

to obtain a resin syrup that was clear at elevated and room temperatures. It had an excellent-cure alone and a very last cure with alpha, beta-dichloropropionitrile. A molding compound from 55 parts of the syrup (based on the resin solids conte t thereof) and 45 parts alpha flock had an exce ent hard cure and good flow and the molded piece was light-colored and shiny. Comparable results .were obtained with resins obtained by using the and tri-derivatives in equivalent 1ormula- Example 17 M01 ratio Parts by (sp n-ox.)

weight Managua tit-derivative. (68.5% concentraon A uoons iormsldeh de Gl ycerine. y

were refluxed for15 minutes. The syrupy P duct was clear while hot and also on cooling. At 135 0. it had a. slow but good cure. Ghl'oroacaccelerated and hardened the The syrup was clear smm z 1e Moi ratio Parts by (approx.) weight Aqueous (ii-derivative (61% concentration) i 122. 5 Aqueous formaldehyde 3 84. 8 Butyl alcohol 20% 17. 6 NaOH (in water sol.) 0. i 0. 14

were refluxed for 15 minutes to form a syrup which was clear while hot and also on cooling. It had a 9!! 0:13.95 and a good cure at 135 C. A thin fllm oi the syrup dried at 60-70 C. to a cleanhard resin.

were refluxed for 15 minutes. The syrup product was clear while hot but changed to a white paste on cooling. At 135' C. the paste melted to a. clear melt which was self-curing. The cure was prololiled but 800d.

(B) The tollowins:

Moi ratio Parts by pp -l eisht Aqueous didc'lvative 00% concentration)" 1 75.7 A iornaldahyd 5 74.2 {I mloliate 6% 2. 5 NaO (in water) 0.01 0.07

were refluxed tor minutes. The syrup was clear while hot and cloudy at room temperature.

It had an excellent cure.

(C) The following:

Mol ratio Parts by (approx.) weight AM trldadvative 6.5 concentration) 1 36. 5 A lormaldehyd 7 40.9 it mamas 0% 1. 8 NaO (in water) 0. 01 0. 03

were refluxed lot 15 minutes to term a syrup that was clear while hot and at room temperatures andwhichhadasoodcureatmyc Example M01 ratio Parts by PX A mouodcivative (07% couooutrs- 1 63 7 A 3 4213 The above were refluxed together for 15 minu. The syrup was clear while hot but precipitatad on cooling. It had a pH of 7.8 and a slow but Iood cure at 136' c.

iii

Aqueous di-derivativc (66% cone nuances (A) The ioilowing:

Moi ratio (approx) Aoetamide s Aqueous formaldehydo.. I; I Aqueous NH: (28%) it 0. 39

"were refluxed for 15 The resu' syrup having a pH of 2 .3 clear while ho; very thick and white on cooling. At 135 C. its cure was excellent with long, tacky stage. Chloroaoetamide greatly accelerated and hardened the cure.

(Bi following:

Moi ratio Parts by (approx) weight Aqueous tri-dcrivative (63.5% concentration) 1 5 Aqueous formaldehyde t 7 40. {i Acetomido 5% 1.8 NaOH (in water) 0.01 0. 03

. mum gloss and water resistance and minimum molding time are desired.

In producing any of these new condensation products, the choice of the aldehyde component is dependent largely upon economic considerations and the particular properties desired in the finished product. I prefer to use as the aldehyde reactant, formaldehyde or compounds engendering formaldehyde, e. g.-, paraformaldehyde, hexamethylene tetramine, etc. For some applications I may use, for instance, acetaldehyde, propionaldehyde, butyraldehyde, acrolein, methacrolein, crotonaldehyde, benzaldehyde, furfuraL. etc., mixtures thereof, or mixtures 01 formaldehyde (or compounds engendering formaldehyde) with such aldehydes. Various aldehyde-addition products may be used instead of aldehydes. Such products include the monoand poly (N-carbinol) derivatives, more particularly the monoand polymethyloi derivatives, of urea, thiourea, selenourea, and iminourea, substituted ureas, thicureas, selenoureas, and iminoureas, amides of polycarboxylic acids, e. 8., maleic, itaconic, fumaric, adipic, malonic, citric, phthalic, etc. I may also use with particularly good results, the methylol amino triazines, e. g., mono-, di-, tri-, tetra-, penta-, and hexa-methylol melamines; the methylol amino diazines, e. g., trimethylol 1,3,5-triamino pyridimine; the amino triazoles, e. 3., dimethylol guanazole, etc. mixtures of these materials or mixtures of an aldehyde with such materials may also be used.

The ratio of aldehydic reactant to the melamine derivatives of this invention may he'vaiied over a widerange but ordinarily isoi' the order corresponding to at least one mol of the aldehyde, or an equivalent amount of an aldehyde engenderingor addition products, for each mol of the melamine derivative. Thus, I may use for assesses example from one to seven'or eight mols, pref erably from three to seven mole, of an aldehyde for each mol of the derivative. 'In producing these various condensationproducts, dyes, pigments, plasticizer, mold lubricants; opacifiers,-and various fillers, (e. g.; wood flour,

' glass fibers, asbestos, mineral wool, mica, cloth cuttings, etc) may be compounded with the resin in accordance with conventional practice to provide various thermoplastic and thermosettingmolding compositions. The modified or unmodified resinous compositions of this invention have a wide variety of uses. For example, in addition to their use in the production of molding compositions, they may be used as modifiers of other natural and synthetic resins, as laminating varnishes in the production of laminated articles wherein sheet materials, e. g., paper, cloth, sheet asbestos, etc. are coated and impregnated with the resin, superimposed and thereafter united under heat and pressure. They may be used in the production of wire or baking enamels, for bonding or cementing to'gethermica. flakes to form a laminated mica' .article, for bonding together abrasive grains a J N where Y'-is a member of. the class consisting of Oxygen and sulphur, at least one R represents hydrogen and the other (R.)s represent members of the class consisting of hydrogen, monovalent hydrocarbon radicals and halogeno-hydrocarbon radicals, R is a member of the class consisting of hydrogen and m'onovalenthydrocarbon radicals of not more than six carbon atoms, R" represents a member of the class consisting of hy-' drogen, monovalent hydrocarbon radicals and monovalent halogeno-hydrocarbon radicals, and n is an integer and is at least 1 and not more than 3.

2. A composition as'in claim 1 wherein the aldehyde is formaldehyde.

3. A composition comprising the condensation product of ingredients comprising an aldehyde and an organic compound of the formula wherein Y isa member of the class consisting of oxygen and sulphur, R, R and R" represent hydrogen, and n is an integer and is at least one but not more than 3, p

f 4. A'composition comprising. a condensation product of ingredients comprising an aldehyde and an organic compound corresponding to the formula I (am-or'ma-onak- N/ \N R")t-n -HN fins? wherein Y represents oxygen, R, R and R" represent hydrogen, and n is an integer and mat least one and not more than 3.

5. A composition comprising the condensation product of ingredients comprising an aldehyde and an organic compound corresponding to the formula i N \N LEW) 1-.

wherein Y represents a member of the class consisting of oxygen and sulphur, R and R represent hydrogen, R" represents a monovalent hydrocarbon and radical, and n is an integer and is at least one but not more than 3.

6. A resinous composition comprising the prod.

uct of reaction of ingredients comprising an organic compound having the general formula wherein n is an integer and is at least one but not more than 3, and formaldehyde.

7. A composition as in claim 1 wherein the reaction product is a urea-modified product of the stated components.

8.' A heat-curable composition comprising the heat-convertible product of reaction of (1) a partial condensation product of ingredients comprising an aldehyde and an organic compoundof \N I K l'n all liar where Y isamember of the class consisting of oxygen and sulphur, at least one B represents hydrogen and the other (R)s' represent members of the-class consisting of hydrogen. monovalent hydrocarbon radical and halogeno-hydrocarbon radicals, R is a member of theclass consist n of hydrogen and" monovalent hydrocarbon radicals of not more than six carbon atoms, R" represents a member of the class consisting of hydrogen, monovalent hydrocarbon radicals and monovalent halogeno-hydrocarbon radicals, and

n is an'inteser and is, at least one but not more than 3, and (2)- an alpha, beta-chloropropionitrile.

9. A product comprising the heat-cured com-- position of claim 8.

10. A composition comprising the reaction product of an aldehyde, an organic compound of the formula where Y is a member or the class consisting of oxygen and sulphur, at least one R represents hydrogen and the other (Rls represent members of the class consisting of hydrogen, monovalent hydrocarbon radicals and halogeno-hydrocarbon n is an integer and is at least one but not more than 3 and an organic compound selected from the group consisting of substituted and unsubstituted mono-, di-, and tri-(carbamidomethyl) amines and substituted and unsubstituted mono-,

diand tri- (monocarbinolureidomethyi) amines.

1'1. Themethod of preparing newvcondensation products which comprises eflecting reaction between ingredients comprising an aldehyde and an organic compound corresponding to the formula "*{Qi t mj (ihN-CY-NR-CHR where Y is a member of the class consisting of oxygen andsulphur, at least one It represents assaeas vdros'en and the other (Bis represent members or the class consisting of hydrogen, monovalent hydrocarbon radicals and halogeno-hydrocarbon radicals, R is a member of the class consisting of hydrogen and monovalent hydrocarbon radicals of not more than six carbon atoms, R" represents a member or the class consistingot hydrogen, monovalent hydrocarbon radicals and monovalent halogeno-hydrocarbon radicals, and n is an integer and is at least than 3.

12. The method which comprises condensing a mono-(N carbinol) urea with a melamine in aqueous solution to form a compound corresponding to the formula atoms,'R" representsa member or the class consisting oi. hydrogen, monovalent hydrocarbon radicals and monovalent halogeno-hydrocarbon radicals, and n is an integer and is at least one but not more than 3, mixing said compound with ingredients comprising an aldehyde and heating said mixture to form a resinous composition comprising the reaction product or said compound and said aldehyde. v

' GAETANO F. D'AIELIO.

one but not more.

CERTIFICATE OF CORRECT-ION. Patenen 2, 59,625. January 1 191A.

' GAETANO F. D'AIELIO.

It is hereby certified that error appears in the printed epecifieation of the abo'v'e numbered patel a requiring correcti on as fellows: Page 1, sec opd column, line 50, for "propljcarread propylcarpage 2, first cell min, 113 25, for "aldye' re ad -aldehyd e-;- line fer -"methytlol" read methylol--; page 14., second column, lihe 6, in the table, last "001-; 135m thereof, for "20"- read --'75-; page 6, sec ohd. go-lfimn, line 65,- fer 'pyridimine' read ---py rimidinepage 7, seeend solemn 1, iine 29, strike out "and" first c'currence; and that the saidLettere Patient should lpyread.

with this correction (herein that. the" ewe may conform-to the recerd of the case in the Patent Office; I I

Signed'and sealed this 18111 day qf April, A. I). 191414..

Leslie Frazer (Seal) Acti'ng commssioher 'of Pawnee} 

